Germyl methyl

Reaction of methanetellurol with lithium aluminum hydride in diethyl ether caused liberation of hydrogen and formation of lithium tetrakis[methyltelluro]aluminate. This compound was not isolated but reacted with silyl or germyl halides to give silyl or germyl methyl tellurium derivatives4. 

Excess methyl trimethylsilyl tellurium with dimethyl germyl dichloride produced dimeth-ylgermylene bis [methyl tellurium] in 89% yield. Use of equimolar amounts of the reactants formed mainly dimethyl(chloro)germyl methyl tellurium2. 

Indazole, 5,5-dimethyl-3-trifluoromethyl-4,5-dihydro-trichomonacidal activity, 5, 291 Indazole, 2-ethoxycarbonyl-reactions, 5, 269 Indazole, 3-fluoro-synthesis, S, 263 Indazole, 1-germyl-synthesis, 5, 236 Indazole, 1-glycosyl-synthesis, 5, 289 Indazole, 2-glycosyl-synthesis, 5, 289 Indazole, halo-reactions, S, 266 Indazole, 2-hydroxy-methylation, 5, 269 Indazole, 3-hydroxy-reactions, S, 264 Indazole, 6-hydroxy-diazo coupling, 5, 86 Indazole, hydroxyphenyl-synthesis, S, 288 Indazole, 3-iodo-synthesis, S, 241 Indazole, l-isopropyl-3-phenyl-reduction, 5, 243 Indazole, 3-mercapto-1 -substituted tautomerism, 5, 265 Indazole, methoxy-... 

Lithiation of the germyl hydride S -3 with BuLi in ether and subsequent protonolysis led to recovered hydride of [a]o — 18.5 (86% retention)2. It is assumed that both steps proceed with predominant retention of configuration. Carboxylation of the lithio derivative afforded the carboxylic acid R-12, also with retention of configuration (Scheme 4). The corresponding methyl ester underwent decarbonylation upon heating to afford the methoxy derivative R-15, which was subsequently reduced with LiAlH4 to the (—)-hydride S-... 

The assignment of configuration to these products was made by analogy with the R = CH3 system9. In that case, the two methylated enantiomers were compared with an authentic sample prepared from the known germyl hydride R-5 via the chloro derivative as outlined in equation 5. 

Studies of Equilibria and Shift Reagents.—N.m.r. studies of the exchange of halogen in boron trihalide adducts of trimethylphosphine, its oxide, and sulphide,49 and exchange of chloro- and methoxy-groups between methylphosphino and methyl-silyl or -germyl moieties,80 have been reported. The rates of ionization of phosphoranes... 

The X-ray analysis of diphenylbis[tris(trimethylsilyl)germyl]plumbane, obtained from the reaction of diphenyldichlorolead with the appropriate germyllithium (equation 131), showed a staggering of methyl groups around the lead center154. 

In the presence of air at 5 °C, reaction of HGeCl3 with MA occurs in a different manner to give quantitatively the double germylation product rraws-9,10-bis(trichlorogermyl)-9-methyl-9,10-dihydroanthracene 35 (equation 33). A trans-configuration for 36 was suggested on the basis of comparison with an authentic sample of the ds-isomer obtained alternatively. This configuration is not sterically hindered and its formation can be ascribed to any mechanism. 

The methylated isomers 36 and 39 have different melting points and XH NMR spectra. Since compound 39 was obtained from 37, which has a cA-configuration of the two germyl groups about the central cyclohexane ring, the structure of 39 was assumed to be that of a cA-isomer. Consequently, the fraws-structure was assigned for compounds 35 and 36. 

The two compounds 62 and 63 were isolated and characterized. As in the previously described examples, methylation of the chlorides by MeMgBr proceeded smoothly without any side reactions in which germyl groups are split off. 

The germyl- and silyl-substituted adrenaline derivative 3,4-bis(trimethylsiloxy)-4-a-(trimethylsiloxy)-/ -(methyl)(triethylgermylamino)ethylbenzene (0.1 mgkg-1, i.v.) increased the blood pressure twice as effectively than the same dose of adrenaline. This compound is 7 times less toxic than adrenaline63. 

Jolly, W. L. The Symmetrical Deformation Frequencies of Methyl, Silyl, and Germyl Groups. J. Amer. chem. Soc. 85, 3083—3085 (1963). 

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